EP2900707B1 - Catalyst components for the polymerization of olefins and catalysts therefrom obtained - Google Patents
Catalyst components for the polymerization of olefins and catalysts therefrom obtained Download PDFInfo
- Publication number
- EP2900707B1 EP2900707B1 EP13774374.6A EP13774374A EP2900707B1 EP 2900707 B1 EP2900707 B1 EP 2900707B1 EP 13774374 A EP13774374 A EP 13774374A EP 2900707 B1 EP2900707 B1 EP 2900707B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solid catalyst
- catalyst component
- compound
- polymerization
- esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims description 45
- 238000006116 polymerization reaction Methods 0.000 title claims description 29
- 150000001336 alkenes Chemical class 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims description 49
- 239000011949 solid catalyst Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- -1 hydrocarbyl radical Chemical group 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007860 aryl ester derivatives Chemical class 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000002311 glutaric acids Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002689 maleic acids Chemical class 0.000 claims description 2
- 150000002691 malonic acids Chemical class 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 150000003890 succinate salts Chemical class 0.000 claims description 2
- 150000003444 succinic acids Chemical class 0.000 claims description 2
- 235000011044 succinic acid Nutrition 0.000 claims 1
- 239000011701 zinc Substances 0.000 description 64
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 44
- 239000011777 magnesium Substances 0.000 description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 18
- 229910003074 TiCl4 Inorganic materials 0.000 description 17
- 229910001629 magnesium chloride Inorganic materials 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 239000011592 zinc chloride Substances 0.000 description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 13
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 235000011147 magnesium chloride Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 230000000707 stereoselective effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012721 stereospecific polymerization Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- PJSFQEVODHCOOF-UHFFFAOYSA-N (2-ethylpiperidin-1-yl)-dimethoxy-(3,3,3-trifluoropropyl)silane Chemical compound CCC1CCCCN1[Si](CCC(F)(F)F)(OC)OC PJSFQEVODHCOOF-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- UVGKQRAGAYVWQV-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C(C)C UVGKQRAGAYVWQV-UHFFFAOYSA-N 0.000 description 1
- JZKPTDKULQOZFX-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl-(2-ethylpiperidin-1-yl)-dimethoxysilane Chemical compound CCC1CCCCN1[Si](OC)(OC)C(C)(C)C(C)C JZKPTDKULQOZFX-UHFFFAOYSA-N 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-UHFFFAOYSA-N 0.000 description 1
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical class C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 description 1
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical compound C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- AZSQEXSKABOCGN-UHFFFAOYSA-M CC[Al+]CC.[Cl-].Cl.Cl.Cl Chemical compound CC[Al+]CC.[Cl-].Cl.Cl.Cl AZSQEXSKABOCGN-UHFFFAOYSA-M 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- WGFNXLQURMLAGC-UHFFFAOYSA-N diethyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCC WGFNXLQURMLAGC-UHFFFAOYSA-N 0.000 description 1
- BYQFBFWERHXONI-UHFFFAOYSA-N diethyl 2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C(C)C)C(=O)OCC BYQFBFWERHXONI-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NIOVJFCCEONHGJ-UHFFFAOYSA-N tert-butyl-(2-ethylpiperidin-1-yl)-dimethoxysilane Chemical compound CCC1CCCCN1[Si](OC)(OC)C(C)(C)C NIOVJFCCEONHGJ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003221 volumetric titration Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
Definitions
- the present invention relates to catalyst components for the polymerization of olefins, in particular propylene, comprising a Mg, Zn, Ti and halogen elements and at least an electron donor compound.
- the present invention further relates to the catalysts obtained from said components and to their use in processes for the (co)polymerization of olefins in particular propylene.
- Catalyst components for the stereospecific polymerization of olefins, such as propylene, are widely known in the art and they are of the Ziegler-Natta category type.
- the first catalyst of this type widely used in the industry was based on the use of solid TiCl 3 obtained by reduction of TiCl 4 with aluminum alkyls. The activity and stereospecificity of the catalysts were not so high so that the polymer had to be subject to a deashing treatment to remove the catalyst residues and to a washing step for removing the atactic polymer produced.
- the most spread out catalyst family used industrially comprises a solid catalyst component, constituted by a magnesium dihalide on which are supported a titanium compound and an internal electron donor compound, used in combination with an Al-alkyl compound.
- the titanium atoms in the solid catalyst component have a +4 oxidation state.
- these catalysts are used together with an external donor (for example an alkoxysilane) which helps in obtaining higher isotacticity.
- an external donor for example an alkoxysilane
- One of the preferred classes of internal donors is constituted by the esters of phthalic acid, diisobutylphthalate being the most used.
- the phthalates are used as internal donors in combination with alkylalkoxysilanes as external donor.
- This catalyst system is capable of giving good performances in terms of activity, and propylene polymers with high isotacticity and xylene insolubility. It is however of general interest the possibility of increasing the xylene insolubility particularly for catalyst components based on donors different from phthalates.
- the catalyst shows an increased activity up to about 2% of Zn content; however, the effect on stereospecificity is minimal as the amount of boiling heptane insoluble fraction remains always below 90% and when the amount of Zn approaches 2% wt the heptane insoluble fraction dramatically drops to less than 80%.
- a solid catalyst component comprising Ti, Mg, Zn, Cl, and an electron donor compound characterized by the fact that more than 50% of the titanium atoms are in the +4 valence state, and that the amount of Zn ranges from 0.2 to 3.5 % based on then total weight of said solid catalyst component.
- the Zn compound is selected from the group consisting of Zn halides, Zn carbonate, Zn acetate, Zn nitrate, Zn oxide, Zn sulphate, and Zn sulfide.
- the Zn/Mg molar ratio ranges from 0.001 to 0.05.
- the amount of Zn ranges from 0.2 to 3% by weight.
- the Zn/Mg molar ratio can range preferably from 0.004 to 0.03.
- more than 60% and more preferably more than 70% of the titanium atoms are in +4 valence state.
- the total amount of Ti is typically higher than 0.8% and more preferably in the range 1.1- 2.5%wt.
- the particles of solid component have substantially spherical morphology and average diameter comprised between 5 and 150 ⁇ m, preferably from 20 to 100 ⁇ m and more preferably from 30 to 90 ⁇ m.
- particles having substantially spherical morphology those are meant wherein the ratio between the greater axis and the smaller axis is equal to or lower than 1.5 and preferably lower than 1.3.
- the Mg atoms preferably derive from magnesium chloride, preferably from magnesium dichloride and more preferably from magnesium dichloride in active form meaning that it is characterized by X-ray spectra in which the most intense diffraction line which appears in the spectrum of the non-active chloride (lattice distanced of 2,56 ⁇ ) is diminished in intensity and is broadened to such an extent that it becomes totally or partially merged with the reflection line falling at lattice distance (d) of 2.95 ⁇ .
- the single broad peak generated has the maximum of intensity which is shifted towards angles lower than those of the most intense line.
- the titanium atoms preferably derive from titanium compounds of formula Ti(OR) n X 4-n in which n is comprised between 0 and 4; X is halogen and R is an hydrocarbon radical, preferably alkyl, radical having 1-10 carbon atoms or a COR group.
- titanium compounds having at least one Ti-halogen bond such as titanium tetrahalides or halogenalcoholates.
- Preferred specific titanium compounds are TiCl 4 , and Ti(OEt)Cl 3 .
- the components of the invention also comprise an electron donor compound (internal donor), selected from esters, ethers, amines, silanes and ketones or mixtures thereof.
- an electron donor compound selected from esters, ethers, amines, silanes and ketones or mixtures thereof.
- Particularly preferred classes are alkyl and aryl esters of optionally substituted aromatic mono or polycarboxylic acids such as for example esters of benzoic and phthalic acids, and esters of aliphatic acids selected from malonic, glutaric, succinic and maleic acids.
- Specific examples of esters of aromatic mono or polycarboxylic acids are n-butylphthalate, di-isobutylphthalate, di-n-octylphthalate, ethyl-benzoate and p-ethoxy ethyl-benzoate.
- esters of aliphatic acids preferred are the polycarboxylic acids such as malonates and glutarates.
- diesters disclosed in WO2010/078494 and US 7,388,061 can be used.
- this class particularly preferred are the 2,4-pentanediol dibenzoate derivatives.
- 1,3 diethers of the formula (II) can be advantageously used also the 1,3 diethers of the formula (II): wherein R, R I , R II , R III , R IV and R V equal or different to each other, are hydrogen or hydrocarbon radicals having from 1 to 18 carbon atoms, and R VI and R VII , equal or different from each other, have the same meaning of R-R V except that they cannot be hydrogen; one or more of the R-R VII groups can be linked to form a cycle.
- the 1,3-diethers in which R VI and R VII are selected from C 1 -C 4 alkyl radicals are particularly preferred.
- the final amount of electron donor compound in the solid catalyst component ranges from 1 to 25% by weight preferably in the range from 3 to 20% by weight.
- the Zn compounds can be selected from Zn halides, Zn carbonate, Zn acetate, Zn nitrate, Zn oxide, Zn sulphate, Zn Sulfide.
- Zn halides preferred are Zn dichloride and Zn bromide.
- the most preferred Zn compounds are Zn oxides and Zn dichloride.
- the preparation of the solid catalyst component can be carried out according to several methods.
- the magnesium dichloride in an anhydrous state, the titanium compound, the Zn compound and the electron donor compounds are milled together under conditions in which activation of the magnesium dichloride occurs.
- the so obtained product can be treated one or more times with an excess of TiCl 4 at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared.
- the product obtained by co-milling the magnesium chloride in an anhydrous state, the titanium compound, the Zn compound and the electron donor compounds are treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene, dichloromethane etc.
- the treatment is carried out for a time between 1 and 4 hours and at temperature of from 40°C to the boiling point of the halogenated hydrocarbon.
- Any Zn compound of the invention can be used in the comilling technique, and ZnO and ZnCl 2 are the most preferred.
- the final amount of Zn preferably range from 0.1 to 1.5% by weight and the preferred internal donors are the alky esters of phthalic acids.
- the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) q-y X y , where q is the valence of titanium and y is a number between 1 and q, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCl 2 •pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
- the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130°C).
- the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in form of spherical particles.
- spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648 .
- the so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5.
- the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (generally 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours.
- the treatment with TiCl 4 can be carried out one or more times.
- the electron donor compound is added in the desired ratios during the treatment with TiCl 4 .
- the Zn compound is incorporated directly into the MgCl 2 •pROH adduct during its preparation.
- the Zn compound can be added at the initial stage of adduct preparation by mixing it together with MgCl 2 and the alcohol.
- Zn compound to be added to the Ti compound is ZnCl 2 while for incorporation directly into the MgCl 2 •pROH adduct both ZnCl 2 and ZnO are equally preferred.
- ZnO it is preferred although not strictly necessary use it in very small particle size and in particular in the form of nano particles i.e, particles having at least one dimension in the range of nanometers.
- the final amount of Zn is preferably in the range of 0.1-2% by weight.
- the solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m 2 /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0.2 cm 3 /g preferably between 0.2 and 0.6 cm 3 /g.
- the porosity (Hg method) due to pores with radius up to 10.000 ⁇ generally ranges from 0.3 to 1.5 cm 3 /g, preferably from 0.45 to 1 cm 3 /g.
- the solid catalyst component has an average particle size ranging from 5 to 120 ⁇ m and more preferably from 10 to 100 ⁇ m.
- the desired electron donor compounds can be added as such or, in an alternative way, can be obtained in situ by using an appropriate precursor capable of being transformed in the desired electron donor compound by means, for example, of known chemical reactions such as etherification, alkylation, esterification, transesterification etc.
- the final amount of the electron donor compound is such that its molar ratio with respect to the TiCl 4 is from 0.01 to 2, preferably from 0.05 to 1.2.
- the solid catalyst components according to the present invention are converted into catalysts for the polymerization of olefins by reacting them with organoaluminum compounds according to known methods.
- the alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt 2 Cl and Al 2 Et 3 Cl 3 , possibly in mixture with the above cited trialkylaluminums.
- Suitable external electron-donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine and ketones.
- Another class of preferred external donor compounds is that of silicon compounds of formula (R 6 ) a (R 7 ) b Si(OR 8 ) c , where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R 6 , R 7 , and R 8 , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
- Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane , (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.
- C donor methylcyclohexyldimethoxysilane
- D donor dicyclopentyldimethoxysilane
- diisopropyldimethoxysilane (2-ethyl
- the silicon compounds in which a is 0, c is 3, R 7 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R 8 is methyl are also preferred.
- Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
- the electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
- the polymerization process can be carried out according to known techniques for example slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, it is possible to carry out the polymerization process in gas-phase operating in one or more fluidized or mechanically agitated bed reactors.
- the polymerization is generally carried out at temperature of from 20 to 120°C, preferably of from 40 to 80°C.
- the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa.
- the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
- the catalyst of the invention show, in propylene homopolymerization an increased activity/stereospecificity balance particularly due to increased stereospecificity compared with prior art catalysts not containing Zn atoms. It has been also observed that the catalyst of the invention show a particularly interesting behavior also in the copolymerization of propylene with minor amounts of ethylene for the preparation of propylene random copolymers (RACO).
- Polypropylene random copolymers, in particular propylene-ethylene random copolymers, produced by Ziegler Natta catalysts are known to have a broad ethylene composition distribution because the ethylene units tend to be incorporated by less stereospecific sites. This results in a higher ethylene content in the lower molecular weight and highly stereoirregular polymer chains and in an increase of the o-xylene soluble (XS) fraction.
- the solid catalyst component of the invention When the solid catalyst component of the invention is used in copolymerization of propylene with ethylene, a decrease of the amount of XS fraction at similar copolymer composition is found with respect to standard ZN catalysts ( Fig. 1 ), without observing a decrease of catalyst activity. Moreover, the solid catalyst component of the invention also shows an enhanced comonomer incorporation in the crystalline fraction together with an improved intramolecular comonomer distribution of ethylene ( Fig. 2 ). This results in an improved XS vs melting temperature (Tm) balance ( Fig. 3 ). This characteristic allows to produce RACOs for various application in which the problems associated with the relatively high content of xylene soluble fraction are minimized.
- the sample was prepared by analytically weighting, in a "Fluxy” platinum crucible", 0.1 ⁇ 0.3 grams of catalyst and 2 grams of lithium metaborate/tetraborate 1/1 mixture. After addition of some drops of KI solution, the crucible is inserted in a special apparatus "Claisse Fluxy" for the complete burning. The residue is collected with a 5% v/v HNO 3 solution and then analyzed via ICP at the following wavelengths: Magnesium, 279.08 nm; Titanium, 368.52 nm; Zinc, 213.86 nm.
- 0.5 ⁇ 2 g of the sample in powder form are dissolved in 100 ⁇ 150 ml of HCl 2.7M in the presence of dry ice to create an inert atmosphere.
- the so obtained solution is then subject to a volumetric titration with a solution of ammonium ferric sulphate 0.1N in water, in the presence of dry ice, using as indicator of the equivalence point ammonium sulfocyanate (25%wt/v water solution).
- the stoichiometric calculations based on the volume of the titration agent consumed give the weight amount of Ti 3+ in the sample.
- the determination of the content of internal donor in the solid catalytic compound was done through gas chromatography.
- the solid component was dissolved in acetone, an internal standard was added, and a sample of the organic phase was analyzed in a gas chromatograph, to determine the amount of donor present at the starting catalyst compound.
- the peak of mmmm pentad in the methyl region at 21.80 ppm was used as internal reference.
- the tacticity was evaluated from integrals of pentads in the methyl region using the microstructure analysis described in literature (" Studies of the stereospecific polymerization mechanism of propylene by a modified Ziegler-Natta catalyst based on 125 MHz 13C n.m.r. spectra" Y. Inoue, Y. Itabashi, R. Chûjô Polymer, 1984, 25, 1640 , and " Two-site model analysis of 13C n.m.r. of polypropylene polymerized by Ziegler-Natta catalyst with external alkoxysilane donors" R. Chûjô, Y. Kogure, T.
- the peak of the S ⁇ carbon (nomenclature according to " Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode " C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10, 536 ) was used as internal reference at 29.9 ppm.
- the samples were dissolved in 1,1,2,2-tetrachloroethane -d2 at 120°C with a 8 % wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1 H- 13 C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
- the product of reactivity ratio r 1 r 2 was calculated according to C. J. Carman ("Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Model" C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 1977, 10, 536 )
- the melt flow rate MIL of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg).
- the flexural modulus of the polymer was determined according to ISO 178. Experimental values are reported in Table 3.
- the melting points of the polymers were measured by Differential Scanning Calorimetry (D.S.C.) on a Perkin Elmer DSC-1 calorimeter, previously calibrated against indium melting points.
- the weight of the samples in every DSC crucible was kept at 6.0 ⁇ 0.5 mg.
- the weighted sample was sealed into aluminium pans and heated to 200°C at 10°C/minute.
- the sample was kept at 200°C for 2 minutes to allow a complete melting of all the crystallites, then cooled to 5°C at 10°C/minute.
- the sample was heated for the second time to 200°C at 10°C/min.
- the peak temperature was taken as the melting temperaturefollowing examples are given in order to further describe and not to limit the present invention.
- Magnesium dichloride anhydrous, di-isobutylphthalate in amounts such to meet the Mg/DIBP molar ratio of 17 were introduced into a four ball mill together with a zinc compound of the type and in an amount as indicated in Table 1.
- the components were milled together at room temperature for 6 h.
- the resulting solid catalyst precursors were treated with an excess of TiCl 4: the temperature was raised to 100°C and maintained for 2 h. Thereafter, stirring was stopped, the solid product was allowed to settled and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh TiCl 4 was added to reach the initial liquid volume again. The mixture was then heated at 120°C and kept at this temperature for 1 hour.
- Microspheroidal MgCl 2 ⁇ pC 2 H 5 OH adduct was prepared according to the method described in Example 2 of WO98/44009 , but operating on larger scale and optionally adding in suitable amounts a zinc compound of the type and in an amount as indicated in Tables 2 and 4.
- the mixture was then heated at temperature in the range of 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- the mixture was then heated at temperature in the range of 110°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- the mixture was then heated at temperature in the range of 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- the autoclave was closed and the desired amount of hydrogen was added (in particular, 2 NL in D donor tests, 1.5 NL in C donor tests and 1.25 NL in tests without external donor were used). Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70°C in about 10 minutes and the polymerization was carried out at this temperature for 2 hours. At the end of the polymerization, the non-reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for 3 hours. Then the polymer was weighed and characterized.
- the milled solid catalyst components were prepared using the general method described above. Their composition and related propylene polymerization performance are indicated in Table 1.
- the solid catalyst components were prepared from spherical adducts MgCl 2 ⁇ pC 2 H 5 OH using the general method described above. Their composition and related propylene polymerization performance are indicated in Tables 2-4.
- a 4-litre steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostating jacket, was purged with nitrogen flow at 70°C for one hour. Then, at 30°C under propylene flow (0.5 bar), a suspension containing 75 ml of anhydrous hexane, 0.76 g of AlEt 3 , 0.063 g of cyclohexylmethyldimethoxysilane (C donor) and 0.004 ⁇ 0.010 g of solid catalyst component, previously precontacted for 5 minutes, was charged. The autoclave was closed; subsequently hydrogen was added (1.5 - 1.8 L) to target MIL (230°C, 2.16Kg) 3 - 4 g/10'.
- the solid catalyst components were prepared from spherical adducts MgCl 2 ⁇ pC 2 H 5 OH using the general method described above. Their composition and related propylene polymerization performance are indicated in Table 6.
- Table 1 Milled solid catalyst components Milling Conditions Solid Catalyst Component Polymerization Zn compound Zn/Mg %mol Mg %wt. Ti %wt. Zn %wt. DIBP %wt. ED type Mileage Kg/g XI %wt. Ex. 1 ZnO 0.3 21.1 1.9 0.2 7.1 C 29 97.2 Ex. 2 0.5 22.1 1.4 0.3 4.8 D 43 98.2 Ex. 3 1.2 21.5 1.5 0.7 6.1 C 33 97.7 Ex.
- DIBP diisobutyl phthalate
- Table 2 Phthalate-based solid catalyst components from spherical adducts Support synthesis Support composition Solid catalyst component Polymerization Zn type Zn/Mg %mol Mg% wt Zn% wt EtOH /Mg m.r. Mg% wt Ti %wt Zn %wt DIBP E D Act.
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Description
- The present invention relates to catalyst components for the polymerization of olefins, in particular propylene, comprising a Mg, Zn, Ti and halogen elements and at least an electron donor compound. The present invention further relates to the catalysts obtained from said components and to their use in processes for the (co)polymerization of olefins in particular propylene.
- Catalyst components for the stereospecific polymerization of olefins, such as propylene, are widely known in the art and they are of the Ziegler-Natta category type. The first catalyst of this type widely used in the industry was based on the use of solid TiCl3 obtained by reduction of TiCl4 with aluminum alkyls. The activity and stereospecificity of the catalysts were not so high so that the polymer had to be subject to a deashing treatment to remove the catalyst residues and to a washing step for removing the atactic polymer produced. Nowadays, the most spread out catalyst family used industrially comprises a solid catalyst component, constituted by a magnesium dihalide on which are supported a titanium compound and an internal electron donor compound, used in combination with an Al-alkyl compound. The titanium atoms in the solid catalyst component have a +4 oxidation state. Conventionally these catalysts are used together with an external donor (for example an alkoxysilane) which helps in obtaining higher isotacticity. One of the preferred classes of internal donors is constituted by the esters of phthalic acid, diisobutylphthalate being the most used. The phthalates are used as internal donors in combination with alkylalkoxysilanes as external donor. This catalyst system is capable of giving good performances in terms of activity, and propylene polymers with high isotacticity and xylene insolubility. It is however of general interest the possibility of increasing the xylene insolubility particularly for catalyst components based on donors different from phthalates. These latter in fact generated some health concerns in the industry and, as a consequence, alternatives classes of donors are being evaluated. It has been generally noted that the alternative classes of donors tend to generate catalysts slightly less stereospecific which in propylene polymerization produces a lower amount of polymer fraction insoluble in xylene. In principle it is possible increasing the stereospecificity by increasing the amount of donor in the catalyst. However, as a downside, the polymerization activity decreases and the balance activity/stereospecificity worsens anyhow.
- Based on this, it would be very convenient to find a way of improving the stereospecificity of a catalyst without decreasing its activity and in particular it would be convenient that this method be of a wide applicability.
- Since the discovery of magnesium chloride based supports numerous attempts have been made to include in it additional compounds with the aim of imparting new or modified properties to the final catalysts.
- In
US 4,613,655 substantial amounts (30% by weight or higher) of different inorganic compounds and, among them ZnO and ZnCl2, are mixed with MgCl2 and then ground in the presence of TiCl4 salts in order to produce a catalyst. Apart from the effect of dilution of MgCl2, the catalyst did not show any improvement in polymerization activity. - An increase in polymerization activity is reported by Fregonese and Bresadola (catalyst system supported on MgCl2 doped with ZnCl2 for olefin polymerization- Journal of Molecular Catalysis A: Chemical 145 (1999) p. 265-271) that discloses the preparation of a catalyst support by mixing metallic Mg and up to 2% of metallic Zn and subsequent reaction with n-BuCl. The so obtained support contains MgCl2 in δ-form and ZnCl2 but also contains a substantial amount of metal-alkyl groups (Table 1). These latter, which appear reduced in amount after reaction with TiCl4 are responsible for the presence of titanium atoms in the reduced +3 oxidation state. In propylene and ethylene polymerization the catalyst shows an increased activity up to about 2% of Zn content; however, the effect on stereospecificity is minimal as the amount of boiling heptane insoluble fraction remains always below 90% and when the amount of Zn approaches 2% wt the heptane insoluble fraction dramatically drops to less than 80%.
- On the other hand, higher amounts of ZnCl2 generates, according to
CN 1631922 , a catalyst, having a support containing mixed Mg-Zn halides in which ZnCl2 constitutes more than 15% based on the total of Mg-Zn halides on which are supported Ti atoms and an electron donor, capable of polymerizing vinyl aromatic monomers such as styrene. Interesting results in ethylene/styrene copolymerization are obtained only when the amount of ZnCl2 used in support preparation was higher than the amount of MgCl2. - Now the applicant has found that it is possible to increase the stereospecific response of catalyst component based on Mg containing support on which are supported titanium atoms and donors by modifying it with specific amounts of Zn compounds and by the proper selection of Ti species.
- It is therefore an object of the present invention a solid catalyst component comprising Ti, Mg, Zn, Cl, and an electron donor compound characterized by the fact that more than 50% of the titanium atoms are in the +4 valence state, and that the amount of Zn ranges from 0.2 to 3.5 % based on then total weight of said solid catalyst component. The Zn compound is selected from the group consisting of Zn halides, Zn carbonate, Zn acetate, Zn nitrate, Zn oxide, Zn sulphate, and Zn sulfide. The Zn/Mg molar ratio ranges from 0.001 to 0.05.
- Preferably, in the catalyst of the present invention the amount of Zn ranges from 0.2 to 3% by weight. The Zn/Mg molar ratio can range preferably from 0.004 to 0.03.
- Preferably, more than 60% and more preferably more than 70% of the titanium atoms are in +4 valence state.
- The total amount of Ti is typically higher than 0.8% and more preferably in the range 1.1- 2.5%wt.
- The particles of solid component have substantially spherical morphology and average diameter comprised between 5 and 150 µm, preferably from 20 to 100 µm and more preferably from 30 to 90 µm. As particles having substantially spherical morphology, those are meant wherein the ratio between the greater axis and the smaller axis is equal to or lower than 1.5 and preferably lower than 1.3.
- The Mg atoms preferably derive from magnesium chloride, preferably from magnesium dichloride and more preferably from magnesium dichloride in active form meaning that it is characterized by X-ray spectra in which the most intense diffraction line which appears in the spectrum of the non-active chloride (lattice distanced of 2,56Å) is diminished in intensity and is broadened to such an extent that it becomes totally or partially merged with the reflection line falling at lattice distance (d) of 2.95Å. When the merging is complete the single broad peak generated has the maximum of intensity which is shifted towards angles lower than those of the most intense line.
- The titanium atoms preferably derive from titanium compounds of formula Ti(OR)nX4-n in which n is comprised between 0 and 4; X is halogen and R is an hydrocarbon radical, preferably alkyl, radical having 1-10 carbon atoms or a COR group. Among them, particularly preferred are titanium compounds having at least one Ti-halogen bond such as titanium tetrahalides or halogenalcoholates. Preferred specific titanium compounds are TiCl4, and Ti(OEt)Cl3.
- The components of the invention also comprise an electron donor compound (internal donor), selected from esters, ethers, amines, silanes and ketones or mixtures thereof. Particularly preferred classes are alkyl and aryl esters of optionally substituted aromatic mono or polycarboxylic acids such as for example esters of benzoic and phthalic acids, and esters of aliphatic acids selected from malonic, glutaric, succinic and maleic acids. Specific examples of esters of aromatic mono or polycarboxylic acids are n-butylphthalate, di-isobutylphthalate, di-n-octylphthalate, ethyl-benzoate and p-ethoxy ethyl-benzoate. Among esters of aliphatic acids, preferred are the polycarboxylic acids such as malonates and glutarates. Moreover also preferred are the (S,S), (R,R) or meso forms of the succinates of formula (I) below
- Moreover, also the diesters disclosed in
WO2010/078494 andUS 7,388,061 can be used. Among this class, particularly preferred are the 2,4-pentanediol dibenzoate derivatives. - Moreover, can be advantageously used also the 1,3 diethers of the formula (II):
- Preferably, the final amount of electron donor compound in the solid catalyst component ranges from 1 to 25% by weight preferably in the range from 3 to 20% by weight.
- In particular the Zn compounds can be selected from Zn halides, Zn carbonate, Zn acetate, Zn nitrate, Zn oxide, Zn sulphate, Zn Sulfide. Among Zn halides, preferred are Zn dichloride and Zn bromide. The most preferred Zn compounds are Zn oxides and Zn dichloride.
- The preparation of the solid catalyst component can be carried out according to several methods.
- According to one of these methods, the magnesium dichloride in an anhydrous state, the titanium compound, the Zn compound and the electron donor compounds are milled together under conditions in which activation of the magnesium dichloride occurs. The so obtained product can be treated one or more times with an excess of TiCl4 at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared. According to a further method, the product obtained by co-milling the magnesium chloride in an anhydrous state, the titanium compound, the Zn compound and the electron donor compounds are treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene, dichloromethane etc. The treatment is carried out for a time between 1 and 4 hours and at temperature of from 40°C to the boiling point of the halogenated hydrocarbon. Any Zn compound of the invention can be used in the comilling technique, and ZnO and ZnCl2 are the most preferred. When using the milling technique for preparing the catalyst component the final amount of Zn preferably range from 0.1 to 1.5% by weight and the preferred internal donors are the alky esters of phthalic acids.
- According to another preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)q-yXy, where q is the valence of titanium and y is a number between 1 and q, preferably TiCl4, with a magnesium chloride deriving from an adduct of formula MgCl2•pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the adduct is mixed with an inert hydrocarbon immiscible with the adduct thereby creating an emulsion which is quickly quenched causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in
USP 4,399,054 andUSP 4,469,648 . The so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4 (generally 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours. The treatment with TiCl4 can be carried out one or more times. The electron donor compound is added in the desired ratios during the treatment with TiCl4. Several ways are available to add the Zn compound. According to one option, the Zn compound is incorporated directly into the MgCl2•pROH adduct during its preparation. In particular, the Zn compound can be added at the initial stage of adduct preparation by mixing it together with MgCl2 and the alcohol. Alternatively, it can be added to the molten adduct before the emulsification step. Preferred Zn compound to be added to the Ti compound is ZnCl2 while for incorporation directly into the MgCl2•pROH adduct both ZnCl2 and ZnO are equally preferred. When using ZnO it is preferred although not strictly necessary use it in very small particle size and in particular in the form of nano particles i.e, particles having at least one dimension in the range of nanometers. When preparing the catalyst according to this procedure the final amount of Zn is preferably in the range of 0.1-2% by weight. - The preparation of catalyst components in spherical form are described for example in European Patent Applications
EP-A-395083 EP-A-553805 EP-A-553806 EPA601525 WO98/44001 - The solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m2/g and preferably between 50 and 400 m2/g, and a total porosity (by B.E.T. method) higher than 0.2 cm3/g preferably between 0.2 and 0.6 cm3/g. The porosity (Hg method) due to pores with radius up to 10.000Å generally ranges from 0.3 to 1.5 cm3/g, preferably from 0.45 to 1 cm3/g.
- The solid catalyst component has an average particle size ranging from 5 to 120 µm and more preferably from 10 to 100 µm.
- As mentioned, in any of these preparation methods the desired electron donor compounds can be added as such or, in an alternative way, can be obtained in situ by using an appropriate precursor capable of being transformed in the desired electron donor compound by means, for example, of known chemical reactions such as etherification, alkylation, esterification, transesterification etc.
- Regardless of the preparation method used, the final amount of the electron donor compound is such that its molar ratio with respect to the TiCl4 is from 0.01 to 2, preferably from 0.05 to 1.2.
- The solid catalyst components according to the present invention are converted into catalysts for the polymerization of olefins by reacting them with organoaluminum compounds according to known methods.
- In particular, an object of the present invention is a catalyst for the polymerization of olefins CH2=CHR, in which R is a hydrocarbyl radical with 1-12 carbon atoms, optionally in mixture with ethylene, comprising the product obtained by contacting:
- (i) the solid catalyst component as disclosed above and
- (ii) an alkylaluminum compound and,
- (iii)an external electron donor compound.
- The alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, possibly in mixture with the above cited trialkylaluminums.
- Suitable external electron-donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine and ketones.
- Another class of preferred external donor compounds is that of silicon compounds of formula (R6)a(R7)bSi(OR8)c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R6, R7, and R8, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R6 and R7 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R8 is a C1-C10 alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane , (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Moreover, the silicon compounds in which a is 0, c is 3, R7 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R8 is methyl are also preferred. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
- The electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
- Therefore, it constitutes a further object of the present invention a process for the (co)polymerization of olefins CH2=CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out in the presence of a catalyst comprising the product of the reaction between:
- (i) the solid catalyst component of the invention;
- (ii) an alkylaluminum compound and,
- (iii)optionally an electron-donor compound (external donor).
- The polymerization process can be carried out according to known techniques for example slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, it is possible to carry out the polymerization process in gas-phase operating in one or more fluidized or mechanically agitated bed reactors.
- The polymerization is generally carried out at temperature of from 20 to 120°C, preferably of from 40 to 80°C. When the polymerization is carried out in gas-phase the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In the bulk polymerization the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
- As already explained, the catalyst of the invention show, in propylene homopolymerization an increased activity/stereospecificity balance particularly due to increased stereospecificity compared with prior art catalysts not containing Zn atoms. It has been also observed that the catalyst of the invention show a particularly interesting behavior also in the copolymerization of propylene with minor amounts of ethylene for the preparation of propylene random copolymers (RACO). Polypropylene random copolymers, in particular propylene-ethylene random copolymers, produced by Ziegler Natta catalysts are known to have a broad ethylene composition distribution because the ethylene units tend to be incorporated by less stereospecific sites. This results in a higher ethylene content in the lower molecular weight and highly stereoirregular polymer chains and in an increase of the o-xylene soluble (XS) fraction.
- When the solid catalyst component of the invention is used in copolymerization of propylene with ethylene, a decrease of the amount of XS fraction at similar copolymer composition is found with respect to standard ZN catalysts (
Fig. 1 ), without observing a decrease of catalyst activity. Moreover, the solid catalyst component of the invention also shows an enhanced comonomer incorporation in the crystalline fraction together with an improved intramolecular comonomer distribution of ethylene (Fig. 2 ). This results in an improved XS vs melting temperature (Tm) balance (Fig. 3 ). This characteristic allows to produce RACOs for various application in which the problems associated with the relatively high content of xylene soluble fraction are minimized. - The following examples are given in order to better illustrate the invention without limiting it.
- The determination of Mg, Ti (TOT) and Zn content in the solid catalyst component has been carried out via inductively coupled plasma emission spectroscopy on "I.C.P Spectrometer ARL Accuris".
- The sample was prepared by analytically weighting, in a "Fluxy" platinum crucible", 0.1÷0.3 grams of catalyst and 2 grams of lithium metaborate/tetraborate 1/1 mixture. After addition of some drops of KI solution, the crucible is inserted in a special apparatus "Claisse Fluxy" for the complete burning. The residue is collected with a 5% v/v HNO3 solution and then analyzed via ICP at the following wavelengths: Magnesium, 279.08 nm; Titanium, 368.52 nm; Zinc, 213.86 nm.
- 0.5÷2 g of the sample in powder form are dissolved in 100÷150 ml of HCl 2.7M in the presence of dry ice to create an inert atmosphere. The so obtained solution is then subject to a volumetric titration with a solution of ammonium ferric sulphate 0.1N in water, in the presence of dry ice, using as indicator of the equivalence point ammonium sulfocyanate (25%wt/v water solution). The stoichiometric calculations based on the volume of the titration agent consumed give the weight amount of Ti3+ in the sample.
- The determination of the content of internal donor in the solid catalytic compound was done through gas chromatography. The solid component was dissolved in acetone, an internal standard was added, and a sample of the organic phase was analyzed in a gas chromatograph, to determine the amount of donor present at the starting catalyst compound.
- 2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomed flask provided with a cooler and a reflux condenser and kept under nitrogen. The obtained mixture was heated to 135°C and was kept under stirring for about 60 minutes. The final solution was allowed to cool to 25°C under continuous stirring, and the insoluble polymer was then filtered. The filtrate was then evaporated in a nitrogen flow at 140°C to reach a constant weight. The content of said xylene-soluble fraction is expressed as a percentage of the original 2.5 grams and then, by difference, the X.I. %.
- The analysis was carried out on xylene insoluble fractions, about 40 mg of polymer were dissolved in 0.5 ml of 1,1,2,2-tetrachloroethane-d2. 13C-NMR spectra were acquired at 120°C on a Bruker AV-600 spectrometer equipped with cryoprobe, operating at 150.91 MHz in the Fourier transform mode. A 90° pulse, 15 seconds of delay between pulses and Composite Pulse Decoupling (CPD, bi_WALTZ_65_64pl sequence) to remove 1H-13C coupling were used. About 512 transients were stored in 64K data points with a spectral window of 9000 Hz. The peak of mmmm pentad in the methyl region at 21.80 ppm was used as internal reference. The tacticity was evaluated from integrals of pentads in the methyl region using the microstructure analysis described in literature ("Studies of the stereospecific polymerization mechanism of propylene by a modified Ziegler-Natta catalyst based on 125 MHz 13C n.m.r. spectra" Y. Inoue, Y. Itabashi, R. Chûjô Polymer, 1984, 25, 1640, and "Two-site model analysis of 13C n.m.r. of polypropylene polymerized by Ziegler-Natta catalyst with external alkoxysilane donors" R. Chûjô, Y. Kogure, T. Väänänen Polymer, 1994, 35, 339). The experimental pentad distribution was fitted using the two-site model described in the second reference. In Table 3 only the mmmm pentad of the portion of polymer generated from the "asymmetric bernoullian site" defined according to Chûjô is reported.
- 13C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with cryoprobe, operating at 160.91 MHz in the Fourier transform mode at 120°C.
- The peak of the Sδδ carbon (nomenclature according to "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode " C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10, 536) was used as internal reference at 29.9 ppm. The samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120°C with a 8 % wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
- The assignments of the spectra, the evaluation of triad distribution and the composition were made according to Kakugo (" Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with δ-titanium trichloride-diethylaluminum chloride" M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, Macromolecules, 1982, 15, 1150) using the following equations:
- The product of reactivity ratio r 1 r 2 was calculated according to C. J. Carman ("Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Model" C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 1977, 10, 536)
- Owing to overlaps in the methyl region between peaks due to stereo sequences and Ethylene containing ones, tacticity of Propylene sequences was not evaluated at the pentad level but was calculated at a triad level in the methine region as PPPmm content. The ratio of the integral of mm-Tββ peak (28.90-29.65 ppm) and the integral of the whole Tββ region (29.80-28.37 ppm) was calculated according to the following equation:
the structures of the relative sequences are represented below: -
- The melt flow rate MIL of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg).
- The flexural modulus of the polymer was determined according to ISO 178. Experimental values are reported in Table 3.
- The melting points of the polymers (Tm) were measured by Differential Scanning Calorimetry (D.S.C.) on a Perkin Elmer DSC-1 calorimeter, previously calibrated against indium melting points. The weight of the samples in every DSC crucible was kept at 6.0 ± 0.5 mg.
- In order to obtain the melting point, the weighted sample was sealed into aluminium pans and heated to 200°C at 10°C/minute. The sample was kept at 200°C for 2 minutes to allow a complete melting of all the crystallites, then cooled to 5°C at 10°C/minute. After standing 2 minutes at 5°C, the sample was heated for the second time to 200°C at 10°C/min. In this second heating run, the peak temperature was taken as the melting temperaturefollowing examples are given in order to further describe and not to limit the present invention.
- Magnesium dichloride anhydrous, di-isobutylphthalate in amounts such to meet the Mg/DIBP molar ratio of 17 were introduced into a four ball mill together with a zinc compound of the type and in an amount as indicated in Table 1. The components were milled together at room temperature for 6 h. The resulting solid catalyst precursors were treated with an excess of TiCl4: the temperature was raised to 100°C and maintained for 2 h. Thereafter, stirring was stopped, the solid product was allowed to settled and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh TiCl4 was added to reach the initial liquid volume again. The mixture was then heated at 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- Microspheroidal MgCl2·pC2H5OH adduct was prepared according to the method described in Example 2 of
WO98/44009 - Into a 500 ml round bottom flask, equipped with mechanical stirrer, cooler and thermometer 300 ml of TiCl4 were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, diisobutyl phthalate and 9.0 g of the spherical adduct (prepared as described above) were sequentially added into the flask. The amount of charged internal donor was such to meet an Mg/donor molar ratio of 8. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh TiCl4 was added to reach the initial liquid volume again. The mixture was then heated at temperature in the range of 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- Into a 500 ml round bottom flask, equipped with mechanical stirrer, cooler and thermometer 300 ml of TiCl4 were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, 9,9-bis(methoxymethyl)fluorene and 9.0 g of the spherical adduct (prepared as described above) were sequentially added into the flask. The amount of charged internal donor was such to meet an Mg/donor molar ratio of 6. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh TiCl4 was added to reach the initial liquid volume again. The mixture was then heated at temperature in the range of 110°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- Into a 500 ml round bottom flask, equipped with mechanical stirrer, cooler and thermometer 300 ml of TiCl4 were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, the internal donor and 9.0 g of the spherical adduct (prepared as described above) were sequentially added into the flask. The amount of charged internal donor was such to meet an Mg/donor molar ratio in the range of 7÷8 depending on donor structure. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh TiCl4 was added to reach the initial liquid volume again. The mixture was then heated at temperature in the range of 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The obtained solid was then dried under vacuum and analyzed.
- A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostating jacket, was purged with nitrogen flow at 70°C for one hour. A suspension containing 75 ml of anhydrous hexane, 0.76 g of AlEt3 (6.66 mmol), 0.33 mmol of external donor and 0.006 ÷ 0.010 g of solid catalyst component, previously precontacted for 5 minutes, was charged. Either dicyclopentyldimethoxysilane, D donor, or cyclohexylmethyldimethoxysilane, C donor, were used as external donor as specified in Tables 1 - 3; some tests were carried out without any external donor (Table 4). The autoclave was closed and the desired amount of hydrogen was added (in particular, 2 NL in D donor tests, 1.5 NL in C donor tests and 1.25 NL in tests without external donor were used). Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70°C in about 10 minutes and the polymerization was carried out at this temperature for 2 hours. At the end of the polymerization, the non-reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for 3 hours. Then the polymer was weighed and characterized.
- The milled solid catalyst components were prepared using the general method described above. Their composition and related propylene polymerization performance are indicated in Table 1.
- The solid catalyst components were prepared from spherical adducts MgCl2·pC2H5OH using the general method described above. Their composition and related propylene polymerization performance are indicated in Tables 2-4.
- A 4-litre steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostating jacket, was purged with nitrogen flow at 70°C for one hour. Then, at 30°C under propylene flow (0.5 bar), a suspension containing 75 ml of anhydrous hexane, 0.76 g of AlEt3, 0.063 g of cyclohexylmethyldimethoxysilane (C donor) and 0.004 ÷ 0.010 g of solid catalyst component, previously precontacted for 5 minutes, was charged. The autoclave was closed; subsequently hydrogen was added (1.5 - 1.8 L) to target MIL (230°C, 2.16Kg) = 3 - 4 g/10'. Then, under stirring, 1.2 kg of liquid propylene together with the required amount of ethylene (4 - 11 g) was fed during the raising of temperature from 30 up to 70°C. The temperature was raised to 70°C in about 10-15 minutes and the polymerization was carried out at this temperature for two hours and ethylene was fed during the polymerization. At the end of the polymerization, the non-reacted monomers were removed; the polymer was recovered and dried at 70°C under vacuum for three hours. Then the polymer was weighed and characterized. Experimental data related propylene/ethylene copolymerizations are reported in Table 5.
- The solid catalyst components were prepared from spherical adducts MgCl2·pC2H5OH using the general method described above. Their composition and related propylene polymerization performance are indicated in Table 6.
Table 1: Milled solid catalyst components Milling Conditions Solid Catalyst Component Polymerization Zn compound Zn/Mg %mol Mg %wt. Ti %wt. Zn %wt. DIBP %wt. ED type Mileage Kg/g XI %wt. Ex. 1 ZnO 0.3 21.1 1.9 0.2 7.1 C 29 97.2 Ex. 2 0.5 22.1 1.4 0.3 4.8 D 43 98.2 Ex. 3 1.2 21.5 1.5 0.7 6.1 C 33 97.7 Ex. 4 2.1 21.8 1.3 1.0 4.8 D 42 98.1 Ex. 5 ZnCl2 0.5 22.3 1.4 0.3 5.2 D 40 98.1 Ex. 6 1.2 21.4 1.7 0.6 5.6 C 38 97.3 C1 none - 20.6 2.1 - 6.8 C 32 96.8 C2 D 39 97.6 DIBP = diisobutyl phthalate Table 2: Phthalate-based solid catalyst components from spherical adducts Support synthesis Support composition Solid catalyst component Polymerization Zn type Zn/Mg %mol Mg% wt Zn% wt EtOH /Mg m.r. Mg% wt Ti %wt Zn %wt DIBP E D Act. Kg/g XI %wt Ex.7 ZnO 0.5 10.6 0.15 2.8 18.8 2.4 0.31 11.5 D 97 99.1 Ex.8 1.0 10.1 0.25 2.9 19.8 2.1 0.51 12.0 C 77 98.1 Ex.9 2.0 8.9 0,45 3.1 19.1 2.1 1.05 11.2 D 101 99.0 Ex.10 3.0 9.3 0.75 2.9 19.8 1.9 1.70 6.9 C 71 98.1 Ex.11 5.0 9.7 1.25 2.8 19.7 1.3 2.83 7.6 D 80 98.8 Ex.12 ZnCl2 1.0 10.5 0.20 3.0 18.7 2.7 0.51 10.0 C 66 98.1 Ex.13 2.0 10.4 0.45 2.9 19.0 2.0 0.92 11.5 D 87 98.9 C3 None - 10.3 - 2.9 18.8 2.9 - 13.6 D 96 98.3 C4 C 83 97.6 C5 ZnCl2 10.0 9.8 2.2 3.1 19.2 1.0 4.7 7.4 D 21 98.3 C6 C 15 97.6 Ex.14 ZnO 1.0 11.6 0.29 2.3 18.8 2.4 0.51 11.8 C 65 98.3 C7 none - 12.2 - 2.1 19.6 2.8 - 10.3 C 67 97.6 Table 3: Flexural modulus of polypropylenes from phthalate-based catalysts PP Ex. N° Zn compound Zn/Mg %mol ED type mmmm XI (%) Flexural Modulus N/mm2 Ex.9 ZnO 2.0 D 98.6 1840 Ex.10 3.0 C 96.9 1660 C3 none - D 98.3 1740 C4 C 96.1 1490 Table 4: Diether-based solid catalyst components from spherical adducts Support Synthesis Support Composition Solid Catalyst Component Polymerization Zn type Zn/ Mg %mo l Mg % wt. Zn % wt. EtOH / Mg m.r. Mg % wt. Ti % wt. Zn % wt. Diether % wt. ED typ e Act. Kg/ g XI %wt Ex. 15 ZnO 1.0 10.1 0.25 2.9 15.1 4.6 0.42 16.4 no ED 141 96.4 Ex. 16 2.0 10.0 0.45 2.8 15.3 4.0 0.85 15.4 D 76 98.8 Ex. 17 ZnCl2 2.0 10.4 0.45 2.9 15.1 4.2 0.74 15.1 D 95 98.6 Ex. 18 no ED 150 96.9 C8 none - 10.2 - 3.0 14.3 5.5 - 16.4 D 84 98.2 C9 no ED 143 96.0 Diether = 9,9-bis(methoxymethyl)fluorine Table 5: Propylene-ethylene copolymerization with phthalate-based solid catalyst components of Table 2 NMR DSC Example Solid Catalyst Component Mileage kg/g XI wt% E wt% EXI wt% [PEP]/[E]XI TmII run °C Ex. 19 Ex. 8 100.5 95.3 2.5 1.83 0.920 150.0 Ex. 20 Ex. 9 90.6 95.6 2.5 1.93 0.911 148.8 Ex. 21 Ex. 9 103.3 92.0 4.2 2.90 0.877 141.7 Ex. 22 Ex. 9 160.2 88.4 5.1 3.64 0.865 138.3 Ex. 23 Ex. 13 79.2 93.1 3.8 2.73 0.885 143.3 C10 C3 82.6 93.2 3.0 2.08 0.887 148.0 C11 C3 93.9 79.8 6.2 4.17 0.827 137.0 Table 6: Solid catalyst components from spherical adducts with different internal donors Support Synthesis Support Composition Solid Catalyst Component Polymerization Zn type Zn/ Mg % mol Mg % wt. Zn % wt. EtOH / Mg m.r. Internal donor name Mg % wt. Ti % wt. Zn % wt. ID % wt. ED Act. Kg/g XI %wt. Ex. 24 ZnO 1.6 10.4 0.40 2.9 Di-n- hexyl 3,3-dimethyl glutarate19.2 2.1 0.81 11.2 D 73 98.9 Ex. 25 C 43 98.1 C12 none - 10.6 - 2.9 17.4 3.0 - 14.7 D 60 97.9 C13 C 46 97.1 Ex. 26 ZnO 1.6 12.4 0.55 2.1 Di-n- hexyl 3,3-dimethyl glutarate20.4 1.8 0.87 7.7 D 58 98.6 Ex. 27 C 44 97.8 C14 none - 12.5 - 2.1 18.6 2.7 - 13.1 D 55 98.0 C15 C 46 97.3 Ex. 28 ZnO 1.0 9.3 0.20 3.1 Diethyl 2-isopropyl malonate 20.6 1.7 0.55 11.6 D 35 98.1 Ex. 29 C 29 97.2 C16 none - 10.8 - 2.8 19.4 3.0 - 11.9 D 28 97.4 C17 C 22 95.9 Ex. 30 ZnO 1.0 9.3 0.20 3.1 Meso diethyl 2,3-diisopropyl succinate19.4 2.6 0.49 11.4 D 56 97.3 C18 none - 10.8 - 2.8 18.9 3.3 - 11.6 D 54 96.7
Claims (11)
- A solid catalyst component for the (co)polymerization of olefins CH2=CHR, in which R is a hydrocarbyl radical with 1-12 carbon atoms, optionally in mixture with ethylene, comprising Ti, Mg, Zn, Cl, and an electron donor compound in which:- the Zn compound is selected from the group consisting of Zn halides, Zn carbonate, Zn acetate, Zn nitrate, Zn oxide, Zn sulphate, Zn Sulfide;- more than 50% of the titanium atoms are in the +4 valence state;- the amount of Zn ranges from 0.2 to 3.5% by weight based on then total weight of said solid catalyst component and- the Zn/Mg molar ratio ranges from 0.001 to 0.05.
- The solid catalyst component of claim 1 in which the amount of Ti ranges from 1.1 to 2.5%wt.
- The solid catalyst component of claim 1 in which electron donor compound is selected from esters, ethers, amines, silanes and ketones or mixtures thereof.
- The solid catalyst component of claim 1 in which electron donor compound is chosen from the group consisting of alkyl and aryl esters of optionally substituted aromatic mono or polycarboxylic, esters of malonic acids, esters of glutaric acids, esters of succinic acids, esters of maleic acids and 1,3 diethers of the formula (II):
- The solid catalyst component of claim 1 in which electron donor compound is chosen from the group consisting of the (S,S), (R,R) or meso forms of the succinates of formula (I) below
- The solid catalyst component of claim 1 in which the final amount of electron donor compound in the solid catalyst component ranges from 1 to 25% by weight.
- The solid catalyst components of claim 1 in which the Zn compounds are selected from Zn oxides and Zn dichloride.
- A catalyst for the polymerization of olefins CH2=CHR, in which R is a hydrocarbyl radical with 1-12 carbon atoms, optionally in mixture with ethylene, comprising the product obtained by contacting:(i) the solid catalyst component according to any of the preceding claims and(ii) an alkylaluminum compound and,(iii) optionally an external electron donor compound.
- The catalyst according to claim 8 in which the alkyl-Al compound (ii) is chosen among the trialkyl aluminum compounds.
- The catalyst according to claim 8 in which the external donor compounds is selected from silicon compounds of formula (R6)a(R7)bSi(OR8)c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R6, R7, and R8, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
- A process for the (co)polymerization of olefins CH2=CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out in the presence of the catalyst according to anyone of claims 8-10.
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BR112015028319B8 (en) * | 2013-05-22 | 2021-07-06 | Borealis Ag | propylene copolymer, injection molded article, thin packaging and copolymer production process |
US10208135B2 (en) | 2014-10-03 | 2019-02-19 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins |
US11021555B2 (en) * | 2016-07-15 | 2021-06-01 | Basell Poliolefine Italia S.R.L. | Catalyst for the polymerization of olefins |
WO2018067367A1 (en) | 2016-10-06 | 2018-04-12 | W.R. Grace & Co.-Conn. | Procatalyst composition made with a combination of internal electron donors |
EP3802630A1 (en) | 2018-06-01 | 2021-04-14 | Dow Global Technologies LLC | Ziegler-natta catalyst for production of polyethylene |
CN112707989B (en) * | 2019-10-25 | 2022-08-19 | 中国石油化工股份有限公司 | Plasticizer-free ethylene-propylene random copolymer and application thereof |
US20220403059A1 (en) | 2019-11-20 | 2022-12-22 | Basell Poliolefine Italia S.R.L. | Process for the preparation of a catalyst component and components therefrom obtained |
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